JP2001006983A - Solid electrolytic capacitor and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a capacitor which uses a solid electrolyte the electric conductivity of which is controlled within an appropriate range and which has a superior impedance characteristic and a highly stable thermal characteristic, such as the soldering property (reflowing property) and can be manufactured through a easy manufacturing process and has superior basic characteristics, such as the capacitance, dielectric loss (tanδ), etc., and a highly stable moisture- resistant characteristic, load-resistant characteristic, etc. SOLUTION: A solid electrolytic capacitor has an electrode in which a solid electrolyte layer of a polymer composed at least of one compound selected from among a compound having a thiophene skeleton having a fibril structure, a compound having a polycyclic sulfide skeleton, a compound having a pyrrole skeleton, a compound having a furan skeleton, and a compound having an aniline skeleton is formed on a dielectric coating film composed of a porous valve-action metal by vapor phase polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solid electrolytic capacitor containing a conductive polymer composition having a fibril structure in a solid electrolyte. The present invention relates to a solid electrolytic capacitor having improved moisture resistance and excellent heat resistance and a method of manufacturing the same.

[0002]

2. Description of the Related Art In a solid electrolytic capacitor, a dielectric oxide film layer is generally formed on an anode substrate made of a metal foil having a large specific surface area which has been subjected to an etching treatment. A layer (hereinafter, abbreviated as a solid electrolyte) is formed, and a conductor layer such as a conductive paste is desirably further formed on an outer surface thereof, and connected to a lead wire to produce a basic element of a capacitor. Next, the entire element is completely sealed with an epoxy resin or the like, and is widely used as a capacitor component in electric products.

In recent years, in order to meet the demands for digitization of electric equipment and speeding up of personal computers, small and large-capacity capacitors and low-impedance capacitors in a high-frequency region have been required for these capacitors. Examples of small and large-capacity capacitors include solid electrolytic capacitors such as aluminum electrolytic capacitors and tantalum electrolytic capacitors. However, since the aluminum electrolytic capacitor uses an ion conductive liquid electrolyte as an electrolytic solution, it has a problem that the impedance in a high frequency region is high and the temperature characteristics are poor. On the other hand, in a tantalum electrolytic capacitor, manganese oxide is used as an electrolyte. However, since the specific resistance of the manganese oxide is relatively high, there is a problem that impedance in a high frequency region is high.

In order to meet these demands, it has been proposed to use a conductive polymer having electron conductivity as a solid electrolyte. A conductive organic polyaniline containing a π-conjugated polymer (Japanese Patent Application Laid-Open Showa 61-2396
No. 17), polypyrrole (Japanese Patent Application Laid-Open No. 61-24062)
No. 5), polythiophene derivatives (JP-A-2-156)
No. 11), dopant-free polyisothianaphthene (Japanese Patent Application Laid-Open No. 62-118509), doped polyisothianaphthene (Japanese Patent Application Laid-Open No. 62-118511), and conductivity of 10 ^-3 to 10 ^Use of an intrinsically conductive polymer having a range of ³ S / cm (JP-A-1-169914) has been proposed.

On the other hand, regarding a method for forming a solid electrolyte,
Conventionally, a method of melting and forming the solid electrolyte as described above on a dielectric layer of a valve metal surface having a fine void structure and a method of producing the conductive polymer on a dielectric layer are known. ing. Specifically, for example, Japanese Patent Application Laid-Open No. 2-1561
In JP-A-1 and JP-A-10-32145, a 3,4-ethylenedioxy-thiophene monomer and an oxidizing agent are preferably added in the form of a solution to the oxide film layer of the metal foil separately or before and after. A method of forming by applying is disclosed.

In Japanese Patent Application Laid-Open No. Hei 7-130579, an oxide film is formed on a valve metal to form a dielectric, and a conductive polymer layer is formed on the dielectric layer to form a solid electrolyte. In the method for manufacturing a solid electrolytic capacitor, a monomer compound solution is applied to the surface of the oxide film and dried to form a solid monomer compound, and then an oxidizing agent solution is brought into contact with the solid monomer compound. A method of forming a conductive polymer layer by a polymerization reaction is disclosed.

JP-A-10-50558 discloses a method for manufacturing a solid electrolytic capacitor in which a capacitor element having an anode member formed with a chemical conversion film is impregnated with a conductive polymer as a cathode electrolyte. A method is disclosed in which a conductive polymer layer is formed in a capacitor element by immersing the conductive polymer layer in a solution in which a monomer and an oxidizing agent that become a conductive polymer by oxidative polymerization are dissolved.

In Japanese Patent Application Laid-Open No. 10-50559, an oxide is precipitated in a capacitor element by immersing the capacitor element in a solution of an oxidizing agent, and then evaporating a solvent component. There is disclosed a technique such as a technique in which a high-temperature load characteristic is improved by immersing the polymer in a solution containing a monomer to become a conductive polymer and causing an oxidizing agent to act on the monomer to polymerize the monomer.

Further, with respect to the formation of a solid electrolyte layer using gas phase polymerization, Japanese Patent Application Laid-Open No. 62-47109 discloses a method of manufacturing a solid electrolytic capacitor using a conductive polymer as a solid electrolyte. A method for manufacturing a solid electrolytic capacitor, characterized by introducing an oxidizing agent and an organic acid into a dielectric layer, and then forming a conductive polymer by vapor phase polymerization in a dielectric layer.

Japanese Patent Application Laid-Open No. 63-102309 discloses a solid electrolytic capacitor in which a composite layer composed of a polymer and a heterocyclic compound polymer layer is laminated, wherein the composite layer is formed by oxidation of the polymer layer. There is disclosed a technique characterized in that the reaction product is formed by reacting an agent with a gas of a five-membered heterocyclic compound.

Japanese Patent Application Laid-Open No. 64-12514 discloses a method of manufacturing a solid electrolytic capacitor using a conductive polymer as a solid electrolyte. There is disclosed a method for manufacturing a solid electrolytic capacitor, characterized in that after a treatment with an oxidizing agent solution containing a salt, a conductive polymer is formed on the dielectric layer by vapor phase polymerization.

In JP-A-3-6217, a conductive polymer layer of polypyrrole is formed on a dielectric film by a gas phase polymerization method using an oxidizing agent, and then a conductive polymer layer is formed on the conductive polymer layer. There is disclosed a method for manufacturing a solid electrolytic capacitor, wherein a conductive polymer layer of polypyrrole is formed by an electrolytic polymerization method.

In Japanese Patent Application Laid-Open No. 10-70043, a dielectric oxide film is formed on the surface of an anode body made of a porous valve metal, and two different liquid phase chemical oxidative polymerizations are further formed on the dielectric oxide film. And a method for manufacturing a solid electrolytic capacitor in which a solid electrolyte layer made of a conductive polymer is formed by using gas phase chemical oxidation polymerization.

As a solid electrolyte formed on a dielectric film, a conductive metal oxide or a conductive polymer, which is basically expected to have a sufficiently high electric conductivity and can be improved, has been attracting attention. If the electric conductivity is higher than the appropriate range, the leakage current value increases significantly, resulting in a short circuit, and if the electric conductivity is low, the frequency characteristics are deteriorated and the capacity is greatly reduced.

Specifically, in the conventional capacitor using a conductive polymer such as polypyrrole, there is a problem that the characteristics of the capacitor greatly fluctuate due to a load resistant to moisture. In addition, there is a great demand for heat resistance in connection with assembling capacitors into electronic circuits. For example, solder heat resistance (reflowability) when connecting capacitor elements to electronic circuits is also considered important, and capacitor elements with high heat resistance are required. It has been demanded. That is, in the prior art, there was a problem in a solid electrolyte produced on an oxide film and a method for producing the same.

The conductive polymer obtained in the examples described in Japanese Patent Application Laid-Open No. 62-47109 has low electric conductivity and is difficult to be applied to a recent solid electrolytic capacitor requiring low impedance. Further, the present invention is distinguished from the present invention in the obtained polymer form and polymerization conditions.

The technique described in JP-A-63-102309 and JP-A-64-12514 is to form a polymer compound film containing an oxidizing agent on a dielectric film, and to form a conductive film on the film. A monomer that gives coalescence is introduced in the gas phase, and a conductive polymer obtained by polymerization there is used as a solid electrolyte.In general, an oxidizing agent is contained in a polymer compound film. Is not sufficient, and the resulting polymer is expected to have low electric conductivity. There is a high possibility that the impedance characteristics required of recent solid electrolytic capacitors will be adversely affected, and there is a need for improvement. Also, these disclosures are distinguished from the present invention by the obtained polymer form (shape) and polymerization conditions.

JP-A-3-6217 and JP-A-10-210
Japanese Patent Application Publication No. -70043 discloses a method for forming a solid electrolyte, which includes a combination of gas phase chemical oxidation polymerization and liquid phase chemical oxidation polymerization or a combination of gas phase chemical oxidation polymerization and electrolytic polymerization. In such a case, equipment for performing the two types of polymerization methods is required, and there is a problem that the cost of the product increases.

[0019]

SUMMARY OF THE INVENTION According to the present invention, electric conductivity is controlled to an appropriate range, excellent impedance characteristics, and high thermal stability such as solder characteristics (reflowability).
A capacitor with a solid electrolyte that can be easily manufactured. The purpose of this capacitor is to develop a capacitor with excellent basic characteristics such as capacitance and dielectric loss (tan δ), and stability such as reflow heat resistance and moisture resistance. .

[0020]

Means for Solving the Problems The present invention provides: [1] A solid in which a polymer solid electrolyte layer having a fibril structure is formed on a dielectric film formed on the surface of a porous valve action metal by vapor phase polymerization. Electrolytic capacitor,

[2] The solid electrolytic capacitor according to the above item [1], wherein the solid electrolyte layer of the polymer is formed leaving a void inside the porous material. [3] The solid electrolyte of the polymer is as follows: Equation (1)
The solid electrolytic capacitor according to the above [1] or [2], which is a conductive polymer including a chemical structure represented by [the compound having a thiophene skeleton] as a repeating unit,

Embedded image (Wherein the substituents R ¹ and R ² are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, R ¹ represents a monovalent group selected from the group consisting of a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group.
Alternatively, the hydrocarbon chains of R ² may be bonded to each other at any position to form at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon cyclic structure together with the carbon atom substituted by such a group. May be formed.
The cyclic bond may optionally contain a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino and the like. Δ is in the range of 0 to 1. Z represents an anion; j represents the valence of Z;
Or 2. )

[4] The solid electrolyte of the polymer is represented by the following general formula (2) [Compound having a polycyclic sulfide skeleton]
The solid electrolytic capacitor according to the above [1] or [2], which is a conductive polymer containing a structure represented by the following as a repeating unit:

Embedded image (Wherein the substituents R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸
Is independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, a cyano group, a primary, secondary, or tertiary group. Grade amino group, CF ₃ group,
Represents a monovalent group selected from the group consisting of a phenyl group and a substituted phenyl group. And the hydrocarbon chains of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are bonded to each other at any position,
Such a group may form a divalent chain which forms a cyclic structure of a saturated or unsaturated hydrocarbon of at least one or more 3- to 7-membered rings together with a carbon atom which is substituted. The cyclic bond may optionally contain a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino and the like. k represents the number of condensed rings surrounded by a thiophene ring and a benzene ring having substituents R ^{3 to} R ⁶ , and is an integer of 0 to 3. The fused ring in the formula may optionally contain nitrogen or N-oxide, but will not have the same number of substituents R ^{3 to} R ⁶ . δ is 0
1 range. Z represents an anion, j represents the valence of Z, and is 1 or 2. )

[5] The above item [1] or [2], wherein the solid electrolyte of the polymer is a conductive polymer containing, as a repeating unit, a structure represented by the following general formula (3) [compound having a pyrrole skeleton]. The solid electrolytic capacitor according to

Embedded image (Wherein, substituents R ⁹ and R ¹⁰ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, , a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ⁹ or R ¹⁰ represents a monovalent group selected from the group consisting of phenyl and substituted phenyl groups with one another Join at any position,
Such a group may form a divalent chain which forms a cyclic structure of a saturated or unsaturated hydrocarbon of at least one or more 3- to 7-membered rings together with a carbon atom which is substituted. The cyclic bond may optionally include a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino, and the like. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. )

[6] The above item [1] or [2], wherein the solid electrolyte of the polymer is a conductive polymer containing, as a repeating unit, a structure represented by the following general formula (4) [compound having a furan skeleton]. The solid electrolytic capacitor according to

Embedded image (Wherein, substituents R ¹¹ and R ¹² are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, , a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ¹¹ or R ¹² represents a monovalent group selected from the group consisting of phenyl and substituted phenyl groups with one another Join at any position,
Such a group may form a divalent chain which forms a cyclic structure of a saturated or unsaturated hydrocarbon of at least one or more 3- to 7-membered rings together with a carbon atom which is substituted. The cyclic bond may optionally contain a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino and the like. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. )

[7] The above item [1] or [2], wherein the solid electrolyte of the polymer is a conductive polymer containing, as a repeating unit, a structure represented by the following general formula (5) [compound having an aniline skeleton]. The solid electrolytic capacitor according to

Embedded image (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester Group, halogen, nitro group, cyano group, primary,
Represents a monovalent group selected from the group consisting of a secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ may be bonded to each other at any position to form a saturated or unsaturated at least one or more 3- to 7-membered ring together with the carbon atom substituted by such groups. A divalent chain forming a cyclic structure of a saturated hydrocarbon may be formed. The cyclic bond may optionally include a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino, and the like. δ ranges from 0 to 1. Z represents an anion, j
Represents a valence of Z and is 1 or 2. )

[8] The solid electrolytic capacitor as described in the above item [1] or [2], wherein the polymer solid electrolyte having a fibril structure contains two or more anions as a dopant. [9] Two types of dopants as a dopant The solid electrolytic capacitor according to the above item [8], wherein at least one of the above anions is a polymer anion or an aromatic sulfonic acid anion, [10] The preceding item [9], wherein the polymer anion is a polymer sulfonic acid anion [11] The solid electrolyte of the polymer has a conductivity of from 0.1 to 0.1.
The solid electrolytic capacitor according to any one of [1] to [10], which is 200 S / cm,

[12] When a polymer solid electrolyte is formed by vapor phase polymerization on a dielectric film formed on the surface of a porous valve metal, a compound having a polymerization initiating ability is previously formed on the dielectric film by a liquid phase. , A polymerizable monomer is introduced in the gas phase and chemically oxidized and polymerized, and then washed or not washed to form a film composition of a polymer having a fibril structure. [13] In the step of introducing the polymerizable monomer in a gaseous phase, the polymerizable monomer is placed on the dielectric film such that the partial pressure of the polymerizable monomer is 1 atm or less. The previous section [1]
[14] The method for producing a solid electrolytic capacitor according to [2], wherein in the step of introducing the polymerizable monomer in a gaseous phase, the dielectric material is pressurized so that the vapor pressure of the polymerizable monomer becomes 1 atm or more. [15] The method for producing a solid electrolytic capacitor according to the above [12], wherein the reaction temperature is in the range of -20 ° C to 300 ° C in the step of introducing a polymerizable monomer in a gas phase and chemically oxidatively polymerizing the same.
The method for producing a solid electrolytic capacitor according to the above [12], wherein the compound having a polymerization initiation ability is a persulfate;
The preceding item [1] selected from dichromates and trivalent iron salts
[17] The method for producing a solid electrolytic capacitor according to [2], wherein in the step of introducing the compound having a polymerization initiating ability onto the dielectric film in a liquid phase, the solution concentration of the compound having a polymerization initiating ability is 0.01 mol / L. The method for producing a solid electrolytic capacitor according to the above [12], which is from 5 to 5 mol / L, and

[18] The film forming composition of a polymer having a fibril structure is formed by repeating 1 to 30 steps of forming the polymer solid electrolyte film forming composition according to the above item [12]. The above object has been achieved by developing a method for manufacturing a solid electrolytic capacitor.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The metal having a valve action that can be used in the present invention is a simple metal such as aluminum, tantalum, niobium, titanium, zirconium, magnesium and silicon, or an alloy thereof. About the form,
Any shape can be used as long as it is in the form of a porous formed body such as an etched rolled foil or a fine powder sintered body.

In the present invention, a conductive polymer having a fibril structure is used as a solid electrolyte. Among the polymerizable monomers used for producing the polymer, a compound having a thiophene skeleton is represented by the following general formula (6)

Embedded image (In the formula, the substituents are the same as those in the general formula (1).)

The compound having a polycyclic sulfide skeleton is represented by the following general formula (7):

Embedded image (In the formula, the substituents are the same as those in the general formula (2).)

The compound having a pyrrole skeleton is represented by the following general formula (8)

Embedded image (In the formula, the substituents are the same as those in the general formula (3).)

The compound having a furan skeleton is represented by the following general formula (9)

Embedded image (In the formula, the substituents are the same as in the general formula (4).)

The compound having an aniline skeleton is represented by the following general formula (10)

Embedded image (Wherein the substituents are the same as those in formula (5)), but are not limited thereto.

As the compound having a thiophene skeleton represented by the general formula (6) used for the polymerizable monomer,
Methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-nonylthiophene, 3-decylthiophene, 3- Fluorothiophene,
3-chlorothiophene, 3-bromothiophene, 3-cyanothiophene, 3,4-dimethylthiophene, 3,4
-Diethylthiophene, 3,4-butylenethiophene,
Derivatives such as 3,4-methylenedioxythiophene and 3,4-ethylenedioxythiophene can be given. These compounds are generally commercially available compounds or known methods (for example, Synthetic Met).
als magazine, 1986, vol. 15, p. 169), but the present invention is not limited to these.

As the compound having a polycyclic sulfide skeleton represented by the general formula (7) used for the polymerizable monomer, specifically, a 1,3-dihydropolycyclic sulfide having k = 0 (alias: 1, A compound having a 3-dihydrobenzo [c] thiophene) skeleton and a compound having a 1,3-dihydronaphtho [2,3-c] thiophene skeleton where k = 1. Furthermore, 1,3-dihydroanthra [2,3-
c] a compound having a thiophene skeleton and a compound having a 1,3-dihydronaphthaseno [2,3-c] thiophene skeleton.
It can be prepared by the method described in Japanese Patent No. 3156. Further, among the substituents R ³ , R ⁴ , R ⁵ and R ⁶ of the polycyclic sulfide compound represented by the general formula (7), two adjacent substituents are mutually bonded by an unsaturated bond to form a condensation product. Also included are compounds that form a system 6-membered ring (ortho substitution). For example, 1,3-dihydronaphtho [1,2-c] thiophene derivative with k = 0, and 1,3-dihydrophenanthra [2,3-c] thiophene derivative with k = 1,
1,3-dihydrotriphenylo [2,3-c] thiophene derivatives, and when k = 2, 1,3-dihydrobenzo [a] anthraceno [7,8-c] thiophene derivatives. .

The condensed ring may optionally contain nitrogen or N-oxide, and when k = 0, 1,3-
Dihydrothieno [3,4-b] quinoxaline, 1,3
-Dihydrothieno [3,4-b] quinoxaline-4-oxide, 1,3-dihydrothieno [3,4-b] quinoxaline-4,9-dioxide and the like, but are not limited thereto.

Examples of the compound having a pyrrole skeleton represented by the general formula (8) used for the polymerizable monomer include 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, and 3-pentyl. Pyrrole, 3
-Hexylpyrrole, 3-heptylpyrrole, 3-octylpyrrole, 3-nonylpyrrole, 3-decylpyrrole, 3-fluoropyrrole, 3-chloropyrrole, 3-
Bromopyrrole, 3-cyanopyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-butylenepyrrole, 3,4-methylenedioxypyrrole,
Derivatives such as 3,4-ethylenedioxypyrrole can be mentioned. These compounds can be prepared commercially or by a known method, but the present invention is not limited to these.

Examples of the compound having a furan skeleton represented by the general formula (9) used in the polymerizable monomer include 3-methylfuran, 3-ethylfuran, 3-propylfuran and 3-methylfuran.
-Butylfuran, 3-pentylfuran, 3-hexylfuran, 3-heptylfuran, 3-octylfuran, 3-
Nonylfuran, 3-decylfuran, 3-fluorofuran, 3-chlorofuran, 3-bromofuran, 3-cyanofuran, 3,4-dimethylfuran, 3,4-diethylfuran, 3,4-butylenefuran, 3,4-methylene Derivatives such as dioxyfuran and 3,4-ethylenedioxyfuran can be given. These compounds can be prepared commercially or by a known method, but the present invention is not limited to these.

The general formula (10) used for the polymerizable monomer
As the compound having an aniline skeleton represented by
Methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-pentylaniline,
2-hexylaniline, 2-heptylaniline, 2-octylaniline, 2-nonylaniline, 2-decylaniline, 2-fluoroaniline, 2-chloroaniline, 2
-Bromoaniline, 2-cyanoaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 3,4-butyleneaniline, 3,4-methylenedioxyaniline,
Derivatives such as 3,4-ethylenedioxyaniline can be exemplified. These compounds are commercially available or can be prepared by a known method, but the present invention is not limited to these.

Further, a solid electrolyte may be formed as a copolymer by optionally using a compound selected from the above compound group. The composition ratio of the polymerizable monomer at that time depends on the polymerization conditions and the like, and preferable composition ratios and polymerization conditions can be confirmed by a simple test.

The oxidizing agent used in the production of the conductive polymer of the present invention may be any oxidizing agent capable of sufficiently performing the dehydrogenative two-electron oxidation reaction or the dehydrogenative four-electron oxidation reaction. Compounds which are inexpensive and easy to handle in production are preferred. Specifically, for example, Fe
Fe (III) -based compounds such as Cl ₃ , FeClO ₄ , and Fe (organic acid anion) salts, or anhydrous aluminum chloride /
Cuprous chloride, cupric compound, silver compound, alkali metal persulfate, ammonium persulfate, peroxides, manganese such as potassium permanganate, 2,3-dichloro-
5,6-dicyano-1,4-benzoquinone (DDQ),
Tetrachloro-1,4-benzoquinone, tetracyano-
Quinones such as 1,4-benzoquinone; halogens such as iodine and bromine; sulfonic acids such as peracid, sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid and amidosulfuric acid; Combinations of agents. Particularly, examples of the combination of the oxidizing agents include a mixed system of a Fe (III) -based compound and H ₂ O _{2 and} a mixed system of a cupric compound and a silver compound.

Among these, examples of the basic compound of the organic acid anion forming the organic acid anion iron (III) salt include organic sulfonic acid or organic carboxylic acid, organic phosphoric acid, and organic boric acid. Specific examples of the organic sulfonic acid include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfo-naphthalene, β-sulfo-naphthalene, naphthalenedisulfonic acid, and alkylnaphthalenesulfonic acid (alkyl group). Butyl, triisopropyl, di-t-butyl and the like).

On the other hand, specific examples of the organic carboxylic acid include:
Acetic acid, propionic acid, benzoic acid, oxalic acid and the like can be mentioned.
Further, in the present invention, polyelectrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfate, poly-α-methyl sulfonic acid, polyethylene sulfonic acid, and polyphosphoric acid are also used. Examples of these organic sulfonic acids or organic carboxylic acids are merely examples, and are not limiting.

Of the above-mentioned oxidizing agents, particularly preferred are trivalent Fe compounds, cuprous chloride compounds, alkali persulfates, ammonium persulfates, manganese acids,
Oxidants containing quinones or mixtures thereof can be suitably used.

In one embodiment, the solid electrolyte of the polymer having a fibril structure formed in the present invention includes a reductant anion of the oxidizing agent produced from the oxidizing agent in the polymer (for example, ammonium persulfate is replaced with an oxidizing agent). , The reductant anion is a sulfate ion, which is produced from the oxidizing agent by the reaction). As another form, an anionic species of a compound constituting an oxidizing agent, for example, PF ₆ ⁻ , SbF ₆ ⁻ , As
F ₆ ^- halide anions such as Group 5B elements, BF ₄ ^-
Halide anions such as Group 3B elements of, I ^-
A halogen anion such as (I ₃ ⁻ ), Br ⁻ , Cl ⁻ , C
lO ₄ ^- such as halogen acid anion, AlCl ₄ ^- and FeC
a Lewis acid anion such as l ₄ ⁻ , SnCl ₅ ⁻ or the like; an inorganic acid anion such as NO ₃ ⁻ , SO ₄ ²⁻ ; or the aforementioned organic sulfonic acid anion such as p-toluenesulfonic acid or naphthalenesulfonic acid; To 5 alkyl-substituted naphthalenesulfonic acid anions, anthraquinonesulfonic acid anions, CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , or C
The carboxylate anions such as F ₃ COO ⁻ and C ₆ H ₅ COO ⁻ can be mentioned.

Further, in the present invention, the dopant in the solid electrolyte includes a second anion other than the anion derived from the oxidizing agent.
A dopant may be included, for example, an organic sulfonate anion, an organic phosphate anion, or the like.
Particularly in the organic sulfonic acid anion, aromatic sulfonic acid anion, aromatic polysulfonic acid anion, organic sulfonic acid anion substituted with OH group or carboxyl group, aliphatic organic sulfonic acid anion having a skeleton of adamantane and the like. Various compounds can be applied. For example,
Examples of organic sulfonic acids include benzenesulfonic acid and p
-Toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfo-naphthalene, β-sulfo-naphthalene, naphthalenedisulfonic acid, alkylnaphthalenesulfonic acid (an alkyl group such as butyl, triisopropyl, and di-t-butyl) Is mentioned.

Further, as other examples, an anion of a sulfoquinone compound having one or more sulfonion groups and a quinone structure in the molecule (hereinafter abbreviated as sulfoquinone anion), an anthracene sulfonate anion, naphthalene sulfonate anion, benzene Sulfonate anions and xylylene disulfonic acid anions (o, p, m) can be exemplified.

The basic skeleton of the sulfoquinone anion includes p-benzoquinone, o-benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2,6-naphthoquinone, 9,10-anthraquinone, 1,4-anthraquinone, 1,2-anthraquinone, 1,4-chrysenequinone, 5,6-chrysenequinone, 6,12-chrysenequinone, acenaphthoquinone, acenaphthenequinone, carforquinone, 2,3-bornanedione, 9,10-phenanthrenequinone, 2,7- Pyrenequinone.

Among them, as the sulfoquinone used in the present invention, a sulfoquinone having a skeleton of anthraquinone, 1,4-naphthoquinone or 2,6-naphthoquinone is preferably used. For example, in the case of anthraquinones, anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1,5-disulfonic acid, anthraquinone-1,4-disulfonic acid, anthraquinone-1,3-disulfonic acid, anthraquinone-
1,6-disulfonic acid, anthraquinone-1,7-disulfonic acid, anthraquinone-1,8-disulfonic acid, anthraquinone-2,6-disulfonic acid, anthraquinone-2,3-disulfonic acid, anthraquinone-2,7-disulfone Acids, anthraquinone-1,4,5-trisulfonic acid, anthraquinone-2,3,6,7-tetrasulfonic acid, alkali metal salts thereof, and ammonium salts thereof can be used.

In the case of 1,4-naphthoquinones, 1,4
-Naphthoquinone-5-sulfonic acid, 1,4-naphthoquinone-6-sulfonic acid, 1,4-naphthoquinone-5,7-
Disulfonic acid, 1,4-naphthoquinone-5,8-disulfonic acid, their alkali metal salts, their ammonium salts, and the like can be used.

In the case of 2,6-naphthoquinones, 2,6
-Naphthoquinone-1-sulfonic acid, 2,6-naphthoquinone-3-sulfonic acid, 2,6-naphthoquinone-4-sulfonic acid, 2,6-naphthoquinone-3,7-disulfonic acid, 2,6-naphthoquinone-4 , 8-disulfonic acid, their alkali metal salts, their ammonium salts, and the like.

Further, examples of the sulfoquinone include industrial dyes such as anthraquinone iris R and anthraquinone violet RN-3RN.
These can also be used in the form of the salts as useful sulfoquinone-based dopants.

Similarly, there may be mentioned polymer electrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyethylene sulfonic acid, polyphosphoric acid, etc., but not limited thereto. However, among these, a high molecular weight or low molecular weight organic sulfonic acid compound or polyphosphoric acid is preferable, and an aromatic sulfonic acid compound is preferably used.

The present invention provides a solid electrolytic capacitor equipped with a fibril-structured conductive polymer preferably containing two or more of the above-mentioned dopants as a dopant in the solid electrolyte.

The partial pressure of the polymerizable monomer used in the production of the conductive polymer of the present invention (when introduced as a mixed gas on the dielectric film) and the atmospheric pressure (adjusted under pressure and introduced onto the dielectric film) Is different depending on the type of the substituent of the compound and the type of the solvent, etc., but generally from 10 ^-3 to 10
A range of atmospheric pressure is desirable, and a range of 10 ^{-2 to} 5 atmospheric pressure is more preferred. The reaction temperature is determined by the type and concentration of each compound having the ability to initiate polymerization, the partial pressure (pressure) of the polymerizable monomer, and the like, and is not particularly limited. It is selected in the temperature range of 250 ° C. Desirably, the temperature is from 0 ° C to 150 ° C, and more preferably from 15 ° C to 100 ° C.

In the production method of the present invention, the solvent for dissolving the polymerizable compound (monomer) used may be a solvent that can dissolve both an oxidizing agent and an electrolyte having a dopant function, or each solvent alone. (THF), dioxane, ethers such as diethyl ether, dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone (NM
P), aprotic solvents such as dimethyl sulfoxide (DMSO), esters such as ethyl acetate and butyl acetate, non-aromatic chlorinated solvents such as chloroform and methylene chloride, nitro compounds such as nitromethane, nitroethane and nitrobenzene; Alternatively, alcohols such as methanol, ethanol, and propanol, organic acids such as formic acid, acetic acid, and propionic acid or acid anhydrides of the organic acids (eg, acetic anhydride), water, and a mixed solvent thereof can be used. . Although the solution concentration varies depending on the type and the kind of such solvents substituents of the compounds having polymerization initiation ability is generally preferably in the range of 10 ^-3 mol / L~10mol / L, also 10 ^-2 mol / L The range of ５5 mol / L is more preferred.

The thickness of the conductive polymer layer produced by using these materials is usually about 0.1 to 0.3 μm as a solid electrolyte layer in one cycle. With or without washing the obtained conductive polymer having a fibril structure, and further performing the same operation on the surface of the obtained conductive polymer having a fibril structure at least twice, practically 5 times It is preferable to repeat to the extent. However, it is not preferable that the solid electrolyte layer has an unnecessarily thick thickness, so that about 20 times is usually sufficient. Preferably, the required solid electrolyte layer can be secured in about 3 to 15 times. In this case, the thickness of the conductive polymer also depends on the pressure of the polymerizable monomer used, the amount of the compound having polymerization initiation ability existing on the dielectric film, the reaction temperature, the reaction time, etc. And it is preferable to confirm in advance. The conductivity of the conductive polymer used in the present invention is 0.1 to
Although it is in the range of 200 S / cm, it is preferably 1 to
100 S / cm, more preferably 10 to 100 S / c
m.

It is preferable to provide a conductive layer on the conductive polymer layer thus formed in order to improve the electrical contact with the cathode lead terminal, for example, a solid of conductive paste or Plating, metal deposition, formation of a conductive resin film, and the like are performed. Thereafter, a cathode lead terminal is further connected to this, and for example, a resin mold, a resin case, a metal outer case, and a resin dipping or the like are applied to complete the product as a capacitor product for various uses.

In the solid electrolytic capacitor of the present invention, as the solid electrolyte on the electrode, for example, as shown in FIG. 1, a conductive polymer in a fibril state is oxidized in the pores of the chemically treated porous valve metal foil. A fibril layered structure is formed on the inside of the cathode and on the outer surface of the metal foil by a plurality of polymerization steps, and they have a space in a part between adjacent layers. Therefore, it is possible to effectively reduce the thermal stress in the upper and lower temperatures. In addition, since pores are also formed on the surface of the conductive polymer, the conductive paste layer for connection can enter into the pores on the outer surface, thereby ensuring good adhesion. Furthermore, the presence of the conductive polymer in the form of fibrils in the micropores and the formation of a space by multiple lamination steps ensure the supply of oxygen and repair the dielectric oxide film during conduction. It is estimated that the ability will be improved.

[0061]

The present invention will be described in detail below with reference to examples. (Example 1) A polyimide solution having a width of 1 mm was applied to a portion having a length of 5 mm on a surface of an aluminum conversion foil having a thickness of 90 μm, a width of 3 mm and a length of 10 mm having a dielectric coating layer of alumina on the surface (double-side coating), It was dried and masked. A 3 mm × 4 mm portion of this aluminum chemical conversion foil was immersed in a 10 wt% aqueous solution of ammonium adipate, and a voltage of 8 V was applied to further form it to form a dielectric oxide film. Next, a 3 mm × 4 mm portion of the foil was immersed in a 2 mol / L aqueous solution of ammonium persulfate, pulled up, and dried at room temperature for 3 minutes. Subsequently, this aluminum conversion foil was placed in a reaction vessel heated to 60 ° C, and 3,4-ethylenedioxy-
Thiophene vapor was introduced to the foil surface and polymerized for 20 minutes. After polymerization, dried in a constant temperature bath at 40 ° C. for 30 minutes,
After that, the 3 mm × 4 mm portion of the aluminum foil was impregnated again with a 2 mol / L ammonium persulfate aqueous solution,
The same polymerization operation was repeated three times, and the finally produced poly (3,4-ethylenedioxy-thiophene) was washed in 50 ° C warm water. After that, it was dried at 100 ° C for 30 minutes,
A conductive polymer layer as a solid electrolyte was formed.

To examine the shape of the conductive polymer, a cross-sectional sample of a foil coated with the polymer was prepared by a cooling method (in liquid nitrogen) and observed by SEM (scanning electron microscope). 1 (with polymer formed) and FIG.
From the comparison and observation of (without polymer formation), it was found that the polymer had a small fibril structure but had a laminated shape of a membrane composed of spherical tufts and / or fibrils. Further, the membrane composed of fibrils has a thickness of 10
It was observed that it was as small as 0 nm. Furthermore, it was found that the surface of the foil coated with the polymer (FIG. 2) was densely covered with the polymer film.

Next, as shown in the schematic diagram of FIG. 4, a conductive polymer layer 4 is formed on the oxide layer 3 of the aluminum foil 1 having the fine holes 2, and then a carbon paste 5 is formed on this portion.
Then, six aluminum foils were laminated by applying a silver paste 5, and the cathode lead terminal 7b was connected, and the anode lead terminal 7a was connected by welding to a portion where the conductive polymer layer was not formed. Further, after sealing the element with epoxy resin 6, a rated voltage was applied at 125 ° C. and aging was performed for 2 hours, thereby completing a total of 30 capacitors.
For these 30 capacitor elements, the capacitance and loss coefficient (tan δ) at 120 Hz, the impedance at the resonance frequency, and the leakage current were measured as initial characteristics. The leakage current was measured one minute after applying the rated voltage. Table 1 shows the average of these measured values and 0.16 μm.
The defective rate and the number of short-circuited products when the leakage current of A (0.002 CV) or more was regarded as a defective product are shown. Here, the average value of the leakage current is a value calculated excluding defective products. Subsequently, a reflow test of the 30 capacitor elements and a moisture resistance test of the capacitor elements were performed. However, the reflow test was performed by passing through a temperature region of 230 ° C. for 30 seconds. The humidity test is 85 ° C and 85% RH.
After leaving for 500 hours under high temperature and high humidity, the leakage current value was measured. Leakage current value in the moisture resistance test is 3.2 μA
(0.04 CV) or more was regarded as defective. Table 2 shows the results.

Example 2 Example 1 was repeated except that ferric sulfate was used instead of ammonium persulfate and 1,3-dihydroisothianaphthene was used instead of 3,4-dioxyethylene-thiophene. 30 in the same manner as in the first embodiment.
Completed capacitors. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

(Example 3) In Example 1, 3,4-
Thirty capacitors were completed in the same manner as in Example 1 except that pyrrole was used instead of ethylenedioxy-thiophene. The characteristics of these capacitor elements were evaluated in Example 1.
And the results are shown in Tables 1 and 2.

(Example 4) In Example 1, 3,4-
Thirty capacitors were completed in the same manner as in Example 1 except that furan was used instead of ethylenedioxy-thiophene. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

(Example 5) In Example 1, 3,4-
Thirty capacitors were completed in the same manner as in Example 1 except that aniline was used instead of ethylenedioxy-thiophene. The characteristics of these capacitor elements were evaluated in Example 1.
And the results are shown in Tables 1 and 2.

(Example 6) In Example 1, 2 mol
/ L ammonium persulfate aqueous solution was added as a compound having a doping ability with sodium anthraquinone-2-sulfonate to a concentration of 0.07 mol / L,
In the same manner as in Example 1, 30 capacitors were completed. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

(Example 7) In Example 1, 3,4-
Thirty capacitors were completed in the same manner as in the example except that a mixed gas of 1 atm was introduced by mixing with argon gas so that the partial pressure of ethylenedioxy-thiophene was 600 mHg. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

(Embodiment 8) In Embodiment 1, 3,4-
Thirty capacitors were completed in the same manner as in Example 1 except that the pressure was adjusted so that the pressure of ethylenedioxy-thiophene became 2 atm, and the pressure-resistant reaction vessel was introduced. The characteristics of these capacitor elements were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

(Comparative Example 1) A capacitor was prepared with reference to JP-A-10-70043, and the characteristics of these capacitor elements were evaluated in the same manner as in Example 1. The results are shown in Table 1.
And Table 2.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

According to the present invention, when a solid electrolyte is formed by vapor phase polymerization on a dielectric film formed on a porous valve metal surface, the solid electrolyte is composed of a conductive polymer having a fibril structure. The conductive polymer layer having a fibril structure may have a layered structure, so that a solid electrolytic capacitor having excellent thermal stress relaxation ability and excellent adhesion to the paste layer can be obtained. Further, according to the present invention, the dielectric oxide film is covered with the conductive polymer composition so as to leave a space in the fine pores of the anode, and a solid electrolyte layer excellent in film repair ability at the time of conduction can be obtained. .
As a result, the initial characteristics (loss coefficient, leakage current, heat resistance,
It is possible to provide a solid electrolytic capacitor element which is excellent not only in equivalent series resistance and impedance in a high frequency region, but also in process simplification and long-term reliability (durability under high temperature and high humidity).

[Brief description of the drawings]

FIG. 1 is a scanning electron micrograph (magnification: 5) of a cross section of an anode aluminum foil having a conductive polymer layer formed thereon in Example 1.
0000).

FIG. 2 is a scanning electron micrograph (magnification: 5, magnification) of the surface of the anode aluminum foil on which the conductive polymer layer is formed in Example 1.
000).

FIG. 3 is a scanning electron micrograph (magnification: 50,000) of a cross section (before polymer formation) of an anode aluminum conversion foil used in an example.

FIG. 4 is a schematic view of an example of a solid electrolytic capacitor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Metal foil 2 Micropore 3 Aluminum oxide layer 4 Solid electrolyte 5 Conductor layer 6 Sealing resin 7a, 7b Lead terminal

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 79/00 C08L 79/00 A 101/06 101/06 H01G 9/02 331H 331F (72) Inventor Toru Sawaguchi Nagano 6850 Omachi, Omachi, Showa Denko Omachi Plant (72) Inventor Atsushi Sakai 6850, Oji, Omachi, Omachi, Nagano Showa Denko Omachi Plant F term (reference) 4J002 BC122 BQ002 CE001 CM011 DD026 DF026 DG036 EF006 EG006 EV236 FD112 FD116 GQ02 4J032 BA03 BA04 BA05 BA08 BA09 BA13 BA14 BB01 BC03 BC12 BD02 CG01 4J043 PA02 QB02 QB03 RA08 SA05 SA14 SA42 SA43 SA52 SA53 SA54 SB01 UA121 XA03 XA04 XA07 XA28 YB05 YB15 ZB24 B38

Claims (18)

[Claims] 1. A solid electrolytic capacitor in which a polymer solid electrolyte layer having a fibril structure is formed on a dielectric film formed on a surface of a porous valve metal by gas phase polymerization. 2. The solid electrolytic capacitor according to claim 1, wherein the solid electrolyte layer of the polymer is formed leaving a void inside the porous body. 3. The polymer according to claim 1, wherein the solid electrolyte of the polymer is a conductive polymer containing a chemical structure represented by the following general formula (1) [compound having a thiophene skeleton] as a repeating unit. Solid electrolytic capacitor. Embedded image (Wherein the substituents R ¹ and R ² are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, R ¹ represents a monovalent group selected from the group consisting of a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group.
Alternatively, the hydrocarbon chains of R ² may be bonded to each other at any position to form at least one or more 3- to 7-membered saturated or unsaturated hydrocarbon cyclic structure together with the carbon atom substituted by such a group. May be formed.
The cyclic bond may optionally contain a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino and the like. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. ) 4. The polymer according to claim 1, wherein the solid electrolyte of the polymer is a conductive polymer containing, as a repeating unit, a structure represented by the following general formula (2) [compound having a polycyclic sulfide skeleton]. Solid electrolytic capacitors. Embedded image (Wherein the substituents R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸
Is independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, a cyano group, a primary, secondary, or tertiary group. Grade amino group, CF ₃ group,
Represents a monovalent group selected from the group consisting of a phenyl group and a substituted phenyl group. And the hydrocarbon chains of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are bonded to each other at any position,
Such a group may form a divalent chain which forms a cyclic structure of a saturated or unsaturated hydrocarbon of at least one or more 3- to 7-membered rings together with a carbon atom which is substituted. The cyclic bond may optionally contain a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino and the like. k represents the number of condensed rings surrounded by a thiophene ring and a benzene ring having substituents R ^{3 to} R ⁶ , and is an integer of 0 to 3. The fused ring in the formula may optionally contain nitrogen or N-oxide, but will not have the same number of substituents R ^{3 to} R ⁶ . δ is 0
1 range. Z represents an anion, j represents the valence of Z, and is 1 or 2. ) 5. The solid electrolyte of the polymer is a conductive polymer containing, as a repeating unit, a structure represented by the following general formula (3) [compound having a pyrrole skeleton].
Or the solid electrolytic capacitor according to 2. Embedded image (Wherein, substituents R ⁹ and R ¹⁰ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, a halogen, a nitro group, , a cyano group, a primary, secondary or tertiary amino group, CF ₃ group, the hydrocarbon chains of the .R ⁹ or R ¹⁰ represents a monovalent group selected from the group consisting of phenyl and substituted phenyl groups with one another Join at any position,
Such a group may form a divalent chain which forms a cyclic structure of a saturated or unsaturated hydrocarbon of at least one or more 3- to 7-membered rings together with a carbon atom which is substituted. The cyclic bond may optionally include a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino, and the like. δ ranges from 0 to 1. Z represents an anion, j represents the valence of Z, and is 1 or 2. ) 6. The solid according to claim 1, wherein the solid electrolyte of the polymer is a conductive polymer containing, as a repeating unit, a structure represented by the following general formula (4) [compound having a furan skeleton]. Electrolytic capacitor. (Wherein the substituents R ¹¹ and R ¹² are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester group, It represents a monovalent group selected from the group consisting of halogen, nitro group, cyano group, primary, secondary or tertiary amino group, CF ₃ group, phenyl group and substituted phenyl group.
The hydrocarbon chains of R ^{11 and} R ¹² are bonded to each other at any position to form a ring structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. May form a divalent chain. The cyclic bond chain includes carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl,
It may optionally contain a bond such as imino. δ ranges from 0 to 1. Z represents an anion, j represents a valence of Z,
1 or 2. ) 7. The solid electrolyte of the polymer is a conductive polymer containing a structure represented by the following general formula (5) [compound having an aniline skeleton] as a repeating unit.
Or the solid electrolytic capacitor according to 2. Embedded image (Wherein, the substituents R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an alkyl ester Group, halogen, nitro group, cyano group, primary,
Represents a monovalent group selected from the group consisting of a secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ may be bonded to each other at any position to form a saturated or unsaturated at least one or more 3- to 7-membered ring together with the carbon atom substituted by such groups. A divalent chain forming a cyclic structure of a saturated hydrocarbon may be formed. The cyclic bond may optionally include a bond such as carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino, and the like. δ ranges from 0 to 1. Z represents an anion, j
Represents a valence of Z and is 1 or 2. ) 8. The solid electrolytic capacitor according to claim 1, wherein the polymer solid electrolyte having a fibril structure contains two or more anions as a dopant. 9. The solid electrolytic capacitor according to claim 8, wherein at least one of the two or more anions as the dopant is a polymer anion or an aromatic sulfonate anion. 10. The solid electrolytic capacitor according to claim 9, wherein the polymer anion is a polymer sulfonate anion. 11. The solid electrolytic capacitor according to claim 1, wherein the conductivity of the polymer solid electrolyte is 0.1 to 200 S / cm. 12. When forming a polymer solid electrolyte by vapor phase polymerization on a dielectric film formed on the surface of a porous valve action metal, a compound having a polymerization initiating ability is preliminarily formed on the dielectric film in a liquid phase. After the introduction, the polymerizable monomer is introduced in the gas phase and chemically oxidized and polymerized, and then washed or not washed to form a film composition of a polymer having a fibril structure. Production method. 13. The step of introducing a polymerizable monomer in a gas phase, wherein the polymerizable monomer is introduced onto the dielectric film such that the partial pressure of the polymerizable monomer is 1 atm or less. Claim 1
3. The method for manufacturing a solid electrolytic capacitor according to item 2. 14. The method according to claim 12, wherein, in the step of introducing the polymerizable monomer in a gas phase, the polymerizable monomer is introduced onto the dielectric film by applying a pressure so that the vapor pressure of the polymerizable monomer becomes 1 atm or more. Method for manufacturing solid electrolytic capacitor. 15. In the step of introducing a polymerizable monomer in a gas phase and performing chemical oxidation polymerization, the reaction temperature is from -20 ° C. to 3 ° C.
The method for producing a solid electrolytic capacitor according to claim 12, wherein the temperature is not higher than 00C. 16. The method according to claim 12, wherein the compound having a polymerization initiation ability is selected from persulfates, dichromates, and trivalent iron salts. 17. In the step of introducing a compound having a polymerization initiating ability into a liquid phase on a dielectric film, the solution concentration of the compound having a polymerization initiating ability is from 0.01 mol / L to 5 mol.
The method of claim 12, wherein the ratio is / L. 18. The method according to claim 12, wherein the step of forming the polymer solid electrolyte film composition is repeated 1 to 30 times to form a polymer film composition having a fibril structure. To manufacture solid electrolytic capacitors.